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Cite this: RSC Adv., 2015, 5, 20521

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A promising alternative solvent of perovskite to

induce rapid crystallization for high-eciency
photovoltaic devices
Minghang Lv,a Xu Dong,a Xiang Fang,a Bencai Lin,abc Shuai Zhang,abc
Jianning Ding*abc and Ningyi Yuan*abc
As solar cell structures based on planar heterojunctions have already demonstrated very impressive
advances in cost-eectiveness and performance, many dierent solvents are being developed and
gradually adopted for high-performance inorganicorganic hybrid perovskite solar cells. Here, we
introduce a simple planar cell conguration with layers prepared in a fully solution-based process, in
which dimethylacetamide (DMAC) serves as an eective precursor solvent that is comparable with

Received 12th December 2014

Accepted 12th February 2015

N,N-dimethylformamide (DMF). The use of DMAC leads to a smooth and dense perovskite lm via onestep deposition, whose ideal morphology enables solar cells to obtain a high power-conversion
eciency of 15.12%. We also studied the eect of dierent solvents through a computation of the

DOI: 10.1039/c4ra16253f

stabilization energy between PbI2, CH3NH3I, and solvent molecules. These results oer insight into the

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promising directions for the development of solvent engineering.

Introduction
Organicinorganic hybrid perovskite solar cells, the latest trend
in photovoltaics, have become more popular with researchers as
a result of the rapid growth in their power-conversion eciency
(PCE) over the past several years. Methyl ammonium lead
halides such as CH3NH3PbI3 and CH3NH3PbIxCl3
x have been
shown to be ecient light harvesters in perovskite solar cells,
with a broad light absorption range in the visible to nearinfrared region, high carrier mobility, and solution processability.1 The common device architecture consists mainly of a
mesoscopic and exible structure and planar heterojunctions
(PHJs).2 The rst solid-state mesoscopic heterojunctioned
perovskite solar cell was reported in 2012 and showed PCE of
10.9%; it comprised a mesoporous Al2O3 thin lm whose surface
was coated with a thin layer of mixed halide perovskite
CH3NH3PbI2Cl.3 Planar-heterojunction-structured perovskite
solar cells, with the active layers deposited by the co-evaporation
technique, showed a maximum PCE of 15.4%.4 The planar
structure is simpler and easier to control than mesostructured
devices, but it is dicult to control the crystallization of perovskite and interface bonding. Zhou et al. reported a device with
planar geometry and PCE of 19.3% by controlling the formation

Center for Low-Dimensional Materials, Micro-Nano Devices and Systems, Changzhou

University, 213164, Jiangsu, China. E-mail: nyyuan@cczu.edu.cn; dingjn@cczu.edu.cn

Jiangsu Collaborative Innovation Center of Photovolatic Science and Engineering,

Changzhou University, 213164, Jiangsu, China

c
Jiangsu Key Laboratory for Photovolatic Engineering and Science, Changzhou
University, 213164, Jiangsu, China

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of the perovskite layer and optimizing interfacial structures,5

thus demonstrating that high-eciency devices can be attained
using planar structures.
With the improvement of perovskite solar cells in recent
years, many methods have been developed for the deposition of
perovskite lms, including the solution-process, dual-source
vapor deposition,6 and vapor-assisted solution process
(VASP).7 The CH3NH3PbI3 lms associated with very impressive
cell eciencies have been prepared by these methods. There is
no doubt that solution-based spin coating of the perovskite
precursor is becoming widely used in device fabrication,8 and it
can be categorized as one-step deposition and two-step
sequential solution deposition.
One-step deposition is a faster and simpler technique
compared to those involving two steps, providing an ecient
and low-cost means to produce high-performance perovskite
solar cells. In previous studies, the formation of perovskite lms
consisted mainly of solvent vaporization, as well as perovskite
crystallization and the sublimation of excess organic components.9 In addition, dierent auxiliary processes and various
relative rates of reactions were involved when dierent
precursor materials and nishing conditions were used, which
also had an impact on the quality of the lms and crystalline
morphology. Both evaporation and crystallization appear to
occur simultaneously during spin coating in the conventional
one-step deposition process. The main problem with spin
coating, however, is that the resulting perovskite lms have
large island structures, many areas with uncovered pin-holes,
and poor surface coverage because of the uncontrolled crystal
growth of perovskite, especially on planar substrates without

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mesoporous scaolds.10 This causes some problems like lightharvesting reduction, charge recombination, lm instability,
and decreased device eciency. Thus, the one-step method still
needs to be improved and further optimized to reduce these
disadvantages.
Much of the earlier studies on perovskite layers were focused
on substrate materials, annealing temperature, heating time,
spin-coating speed, and precursor concentration in one-step
solution deposition. However, researchers have recently discovered that modifying the precursor solution is an ecient way to
improve perovskite lms and to obtain high eciency. Carnie
et al. added Al2O3 nanoparticles directly to the perovskite
precursor solution and attained ecient lead-halide-based
perovskite devices.11 Zhao and coworkers demonstrated a novel
one-step solution approach to prepare perovskite CH3NH3PbI3
lms by adding CH3NH3Cl to the standard CH3NH3PbI3
precursor solution; the results suggest that this new approach is
promising for controlling CH3NH3PbI3 growth to achieve highperformance perovskite solar cells.12 In other words, additives
can participate in the perovskite formation and play multiple
roles in modulating the dynamics of perovskite crystal growth.13
Furthermore, selecting suitable solvents of the precursor is a
very critical step towards the optimization of the perovskite
lm's morphology. Currently, the most commonly used
solvents of the perovskite precursor are N,N-dimethylformamide (DMF) and g-butyrolactone (GBL), with the exception of
dimethylsulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP)
owing to their low volatility. The smooth surface and homogeneous crystal domains of a perovskite lm can be produced by
certain combinations of these solvents, such as DMFGBL,14
GBLDMSO.15 There are also reports of spin coating by releasing
droplets of a second solvent like chlorobenzene (CBZ),8 toluene,
and xylene to induce crystallization, or by the introduction of a
simple gas-assisted method to promote evaporation of the
solvent and accelerate supersaturation of the solution.16
Extremely uniform and dense perovskite layers were formed as a
result. Nevertheless, dimethylacetamide (DMAC), the homologue of DMF, had been overlooked, and it is now emerging as a
promising alternative solvent of perovskite to induce rapid
crystallization of perovskite lms for high-eciency photovoltaic devices.
In this study, we used DMAC as a solvent to promote rapid
crystallization instead of the commonly used DMF to dissolve
the precursor CH3NH3PbI3 and deposit perovskite lms by onestep deposition. This simple solution-based spin coating oers
many advantages: it does not require a second solvent, additives, modication, or external assistance. Employing a DMAC
solution of CH3NH3PbI3, we also developed a strategy for
obtaining a denser and smoother perovskite lm than that
produced with traditional DMF. The interactions between PbI2,
CH3NH3I, and the solvent molecules, including DMAC and
DMF, were further elucidated according to theoretical calculations, showing that DMAC has more appropriate coordinating
ability than DMF. The use of DMAC dramatically improved the
morphology of the perovskite lms, which consisted of threedimensional single grains and one-dimensional crystals. The
resulting perovskites led to a greatly improved short-circuit

20522 | RSC Adv., 2015, 5, 2052120529

Paper

current and an eciency of 15.12% for the best-performing

device with planar structure under standard reporting
conditions.
Materials preparation
All materials were purchased from either Alfa Aesar or
Sigma-Aldrich. CH3NH3I was synthesized by reacting 27.86 ml
methylamine (40% in methanol, Junsei Chemical Co.) and
30 ml hydroiodic acid (57 wt% in water, Aldrich) in a 250 ml
round-bottomed ask at 0  C for 2 h with stirring. The precipitate was recovered by evaporation at 50  C for 1 h. Then, the
product CH3NH3I, was dissolved in ethanol, recrystallized from
diethyl ether, and dried at 60  C in a vacuum oven for 24 h.
Spiro-MeOTAD was purchased from Aldrich.
Solar cell fabrication
Fluorine-doped transparent conducting SnO2-coated glass
substrates (FTO) were cleaned using ultrasonic washing in
ethanol for 30 min and were subsequently treated in an oxygen
plasma cleaning machine for 10 min. A 40 nm-thick compact
layer of TiO2 was then coated on the substrates by a spin coater
at 3000 rpm for 30 s and the lm was annealed at 500  C for
60 min. The synthesized CH3NH3I powder was mixed with PbI2
at a 1 : 1 mol ratio in DMAC or DMF at 65  C for 12 h. The
concentration of CH3NH3PbI3 was 1 mol L
1. The solution was
then coated onto the c-TiO2/FTO substrate by spin-coating at
3000 rpm for 30 s, and dried on a hot plate at 105  C for 10 min.
This steps were carried out in a N2-purged glove box
(<0.1 ppm O2 and H2O). Subsequently, the spiro-OMeTAD-based
hole-transfer layer (170 mg spiro-OMeTAD, 28.5 ml 4-tert-butylpyridine and 20 mg lithium-bis (triuoromethanesulfonyl)
imide (Li-TFSI) all dissolved in 1 ml chlorobenzene) was
deposited by spin coating at 4000 rpm for 30 s. Spiro-OMeTAD
stands for 2,20 ,7,70 -tetrakis(N,N-di-p-methoxyphenilamine)9,90 -spirobiuorene. Finally, a 130 nm thick silver layer was
deposited by vacuum evaporation at a pressure of 1.3  10
3 Pa.
Device characterization
The currentvoltage (JV) curves of the solar cells were measured
under ambient conditions using a Keithley 2400 source meter
(Keithley Instruments Inc., Cleveland, OH, USA). The cells were
illuminated by a 450 W Class AAA simulator equipped with an
AM1.5G lter (XES-40S1) at a calibrated intensity of
100 mW cm
2, as determined by a standard silicon reference
cell. The eective area of the cell was dened as 0.0405 cm2
using a non-reective metal mask. The crystallographic structure of the perovskite was analyzed by X-ray diraction (XRD)
(D/MAX Ultima III, Rigaku Corporation, Tokyo, Japan) using Cu
Ka radiation. The morphology was determined by scanning
electron microscopy (SEM). UV-visible (UV-vis) spectra were
carried out on a Hitachi U-3010 spectrophotometer (Hitachi,
Ltd., Chiyoda, Tokyo, Japan). The external quantum eciency
(EQE) measurements were carried out using a system consisting
of a Xe lamp (300 W) with a monochromator (Oriel 74100). The
light intensity was measured with an optical power meter (Ophir
Optronics 70310) equipped with a calibrated thermopile head

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(Ophir Optronics 71964). Electrochemical impedance spectroscopy (EIS) was conducted using a Zahner IM6ex electrochemical
workstation, in which a perturbation of 10 mV was applied, and
the frequency ranged from 1 Hz to 1 MHz.

Results and discussion

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Computation method
In order to investigate in depth the eect of solvents on the
reaction rates of PbI2 and CH3NH3I as well as the speed of
crystallization of these perovskite materials, we conducted
simulations of PbI2, CH3NH3I, and the solvent molecules DMAC
and DMF. All the calculations were performed using the
GAUSSIAN-03 program. The minimum-energy structures of all
molecular isomers were completely optimized using densityfunctional theory (DFT) employing Becke's three-parameter
exchange potential and the LeeYangParr correlation functional (B3LYP). The LanL2DZ basis set was used for Pb and I
atoms, whereas the 6-311++G(d,p) basis set was used for C, N, O,
and H atoms. Vibrational mode analyses were systematically
carried out to conrm that on a potential energy surface all the
optimized geometries corresponded to a local minimum that
had no imaginary frequency mode. The structural changes of the
molecules under the inuence of foreign water molecules were
examined. To further investigate the strength of the interaction
between the organicinorganic hybrid and water molecules, a
natural bonding orbital (NBO) analysis was carried out. The
interaction energies were corrected for the basis set superposition error (BSSE) using the counterpoise correction method of
Boys and Bernardi.20 In the NBO analysis, the stabilization
energy E(2) for each donor NBO (i) and acceptor NBO (j) associated with delocalization (2e-stabilization) i / j is estimated
as:
E2 DEij qi

connecting bond) can inuence the molecular properties

through delocalization interactions, known as the hyper conjugative eect.

F i; j2
3i
3j

where qi is the occupancy of the donor orbital, 3i and 3j are

diagonal elements (orbital energies), and F(i,j) is the odiagonal NBO Fock matrix element. Vicinal interactions
between the delocalizing acceptor orbital and the orbital of the
adjacent bonded atom (donoracceptor NBOs separated by one

Fig. 1 shows the spin-coating process for the preparation of

perovskite lms, in a glove box, by one-step deposition on
uorine-doped tin oxide (FTO) glass substrates coated with a
compact TiO2 layer. The CH3NH3PbI3 precursor solutions were
based on the solvents DMAC and DMF. For the sample prepared
from the precursor solution with DMAC as the solvent, the
perovskite crystals formed immediately, and the color of the
lm on the substrate changed to light gray during the conventional spin-coating process. The surface appeared smooth and
shiny black when heated. In contrast, for the sample prepared
from the precursor solution with pure DMF as the solvent, the
color change to gray was not observed during the rotations, but
it continued to exhibit a rich yellow color. The lms were subjected to annealing at 100  C for 10 min to remove residual
solvent and to promote crystallization. Moreover, the perovskite
layer surface was rough and inhomogeneous. The above
observations suggest that the DMAC solvent was the more
volatile component for promoting fast nucleation and growth of
crystals in the lm.
Fig. 2a shows XRD patterns of the two samples, with the
perovskite lms exhibiting almost the same crystalline phases
because of the similarities between the two solvents used to
prepare them. The strong diraction peaks of (110), (220), and
(310) at 2q of 14.1 , 28.4 , and 31.81 , respectively, clearly show
that both perovskite lms contained the tetragonal phase.
However, when XRD measurements were performed on these
lms later to explore their stability, dierent XRD patterns were
obtained, as shown by a comparison of XRD spectra of DMACand DMF-based CH3NH3PbI3 lms that were stored in air for two
days (Fig. 2b and c). For the perovskite lm based on DMF, the
(001) diraction peak of PbI2 appeared at 2q 12.65 , but no PbI2
XRD signal could be detected from the perovskite lms based on
DMAC. In general, the presence of this characteristic diraction

Fig. 1 Schematic illustration of spin-coating process for preparing perovskite lms based on a DMAC solution of CH3NH3PbI3 (top); based on a
DMF solution of CH3NH3PbI3 (bottom).

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Fig. 2 X-ray diraction spectra of as-deposited perovskite lms prepared by one-step deposition of DMAC-based precursor and DMF-based
precursor (a); DMF-based (b) and DMAC-based (c) perovskite lms exposed in atmosphere for 2 days. The diraction peaks for the perovskite
material (circles), FTO/glass substrate (rhombuses).

peak of PbI2 indicates degradation of the perovskite structures

under humid environment (45  10% relative humidity).17 Our
results show that the CH3NH3PbI3 lm based on the precursor
dissolved in DMAC was more stable, which may have been related
to the crystalline morphology of perovskite. Whether dierent
solvents aect their stability still needs further study.
To further investigate the reasons behind the dierent
performances of the perovskite lms, scanning electron microscopy (SEM) was conducted to analyze the morphological variations driven by dierent solvents. Fig. 3 compares the surface
morphology of the DMF- and DMAC-based perovskite lms. The
low-magnication SEM images (Fig. 3a and c) clearly show that
the DMAC-based perovskite lm fully covered the surface of the
FTO/glass substrate, whereas the DMF-based lm with dendritic
structure exhibited poor coverage on the substrate. The highresolution SEM image (Fig. 3b) of the DMF-based perovskite
lm reveal that the surface exhibited a heterogeneous morphology
with grain sizes in the range of 100300 nm. In the case of the
DMAC-based perovskite lm, more uniform and denser crystalline perovskite domains are visible in the high-resolution SEM
image (Fig. 3d), which consisted of three-dimensional single

20524 | RSC Adv., 2015, 5, 2052120529

grains (100200 nm) and one-dimensional crystals (>700 nm).

This dierence in morphology may have originated from the
dierences in the nucleation of grains and crystal growth within

Fig. 3 Scanning electron microscopy images of CH3NH3PbI3 perovskite lms obtained from DMF (a and b) and DMAC (c and d) solutions.

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Fig. 4 UV-vis absorption spectra of CH3NH3PbI3 perovskite layers

obtained from one-step deposition of DMAC-based and DMF-based
precursor.

the lms. The DMAC solution of CH3NH3PbI3 had more supersaturation than the DMF solution of CH3NH3PbI3, thereby
promoting the rate of perovskite crystallization with more crystal

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nuclei. The morphologies also illustrate that a degenerative

process resulted in a perovskite lm that was sparser and had
slower growth. Furthermore, the mixed grains with dierent
dimensions in the DMAC-based perovskite lm may have played a
benecial role in improving the carrier mobility, thus enhancing
the photovoltaic properties.
Fig. 4 shows UV-vis absorption spectra of perovskite lms
prepared from dierent precursor solutions. The CH3NH3PbI3
lms based on the precursor dissolved in DMAC showed strong
and ecient perovskite absorption characteristics, with clear
coverage at wavelengths between 350 and 650 nm. These lms
can lead to an improvement in device performance of perovskite
solar cells.18 In contrast, drastically decreased absorption was
observed in the spectra of DMF-based lms, which indicate
their low nucleation rate and low surface coverage.
We fabricated CH3NH3PbI3-based PHJ perovskite solar cells
on a planar TiO2 compact layer on FTO glass; the cells were
constructed with the conguration of glass/FTO/compact
TiO2/CH3NH3PbI3/spiro-OMeTAD/Ag, and all the lm layers
in the solar cells were deposited by spin coating. For
comparison, two types of CH3NH3PbI3 perovskites were
prepared, one from the CH3NH3PbI3DMF precursor and the
other from the CH3NH3PbI3DMAC precursor. The current-

Fig. 5 (a) JV curves for a PHJ solar cell (FTO/c-TiO2/300 nm-thick perovskite layer/Spiro-OMeTAD/Ag); (b) PCE histograms of perovskite solar
cells obtained from the measurements of 25 devices; (c) cross-sectional SEM image of PHJ solar cell containing the perovskite lm prepared
from the DMAC solution.

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Fig. 6 (a) IPCE spectra and (b and c) Nyquist plot of the DMAC-based and DMF-based perovskite solar cells; (d) the variation of Rrec with the
applied bias.

densityvoltage (JV) characteristics of the perovskite solar

cells are shown in Fig. 5a. The best-performing reference
device prepared from DMF showed PCE of 6.86% under standard AM 1.5 sunlight, with a short-circuit current density (JSC)
of 16.4 mA cm
2, an open-circuit voltage (VOC) of 0.89 V, and a
lling factor (FF) of 0.47. The devices containing perovskite
lms prepared from the CH3NH3PbI3DMAC precursor
showed signicant improvements in all of the photovoltaic
parameters, especially the photocurrent. It exhibited high JSC
of 22.8 mA cm
2, VOC of 1.07 V, and FF of 0.62, resulting in a
much improved value of 15.12% for PCE. Our results revealed
that the good photovoltaic performances of the DMAC-based
PHJ devices were mainly attributable to the perovskite lms
deposited from the CH3NH3PbI3DMAC precursor solution.
The uniform, dense perovskite lms with grains of dierent
dimensions resulted in improved light absorption and
photoelectric property. The Fig. 5c shows the SEM crosssectional image of a planar device developed from a DMAC
solution of CH3NH3PbI3. The 40 nm-thick, dense TiO2 layer
acted as an electron-accepting or hole-blocking layer, the

20526 | RSC Adv., 2015, 5, 2052120529

300 nm-thick CH3NH3PbI3 functioned as an active optical

absorption layer, and the 200 nm-thick spiro-OMeTAD
served as a hole-collecting layer. FTO glass and a 130 nm
Ag layer were used as the charge-collecting electrodes. In
Fig. 5b, the reproducibility of the results is shown by a histogram of the average values of PCE for the perovskite solar cells.
Fortunately, about 90% of the cells made from DMACcontaining precursor solution exhibited an overall eciency
of over 13.50% under standard AM 1.5 sunlight. This should be
attributed to the optimized perovskite layer with uniform
thickness and high crystallinity. These results are in contrast
to those in a previous study, where full coverage of the
perovskite lm prepared from a DMF-containing precursor
solution, rather than a DMAC-containing precursor solution,
led to a higher device eciency.19 The dierence in the results
can be explained by the introduction of Cl
in the earlier
work.19 Many studies have provided evidence that the chargecarrier diusion length and lifetime of the active layer can
be increased by simply introducing Cl
into perovskite to
create lattice distortions and prolong the crystal growth.20

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However, the CH3NH3PbI3 precursor we used was a mixture of

CH3NH3I and PbI2, without the addition of PbCl2. Our experiments indicate that it is dicult to use only DMF to control
the perovskite crystallization and homogeneous nucleation.
The DMAC-based depositioncrystallization method allows
control of the dynamics of nucleation and grain growth of
CH3NH3PbI3, which facilitates the formation of more uniform
perovskite lms.
Fig. 6a shows the EQE in the range from 300 nm to 800 nm.
The results suggest that the DMAC-based perovskite solar cells
has a higher EQE value than the DMF-based perovskite solar
cells in wavelength range of 350750 nm. Therefore, the DMACbased PHJ device has a higher JSC. To further investigate the
charge transfer and recombination rates, we carried out EIS
measurements on both DMAC-based and DMF-based perovskite solar cells. Nyquist plots of the devices are shown in Fig. 6b
and (c) with the dierent applied bias. Two arcs of circle are
observed, but no distinct transmission line (TL) behavior, which
is likely due to the very thin TiO2 lms employed.21 The inset in
Fig. 6b and (c) is the high frequency portion and the equivalent
circuit of the spectra, respectively. The series resistance (Rs) is
related to the interface resistance of the FTO electrode.22 The
rst semicircle at high frequency region is assigned to the
recombination of the charge carriers which is modeled by a
contact resistance (Rco) at the perovskite/HTM interface,23 while
the second semicircle in the lower frequency range is associated
with the recombination resistance (Rrec) at the TiO2/perovskite
interface. The main impedance spectra are dominated by a
large semicircle.2426 In compare with the Nyquist plots for
DMAC-based and DMF-based devices, with a forward bias of
0.55 V, the Rco of the two perovskite solar cells are both small,
while the Rrec of DMAC-based perovskite solar cell is higher.
With a forward bias of 0.95 V, the DMAC-based devices has a
lower Rco and a higher Rrec than the DMF-based devices, indicating a lower carrier recombination rate and a higher charge
transfer rate for the DMAC-based perovskite solar cell. Variation
of Rrec with the applied bias is given in Fig. 6d. It shows that the
Rrec decreases for both DMAC-based and DMF-based devices
with increasing bias. Moreover, it is seen that the DMAC-based
perovskite solar cell displays lower recombination, seen by
higher Rrec at comparable bias. The EIS analyses are consistent
with the IV measurements of the perovskite solar cells.
In order to investigate in detail the critical eect of solvents
on the reaction rates of PbI2 and CH3NH3I, as well as the crystallization of the perovskite material, we conducted simulations
of the reactions. The most stable congurations of PbI2 and
CH3NH3I dissolved in DMF and DMAC were calculated, and the
results are shown in Fig. 7a, b, d and e respectively. The
calculations suggest that when PbI2 is dissolved in the solvents
DMF and DMAC, Pb atoms are covalently bonded to O atoms.
The bonding energy between PbI2 and DMF is larger than that
between PbI2 and DMAC, as shown in Table 1. While CH3NH3I
dissolves in both DMF and DMAC, it interacts with the two
solvents through hydrogen bonding. Table 1 lists the stabilization energies (in kcal mol
1) of the main interactions between
CH3NH3I and DMF or DMAC: the stereoelectric interaction
n(O) / s*NH (the lone pair of an O atom and the antibonding
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orbital of an NH bond) and sOC / s*NH (bonding orbital of an

OC bond and the antibonding orbital of an NH bond). The
interaction between CH3NH3I and DMAC is stronger than that
between CH3NH3I and DMF. Fig. 7c and f show clear schematic
diagrams illustrating that when CH3NH3I and PbI2 are dissolved in DMF (or DMAC) at the same time, CH3NH3I and PbI2
can self-assemble to form the organicinorganic hybrid structure CH3NH3PbI3. As shown in Table 1, there are two major
types of local interactions, namely, (1) n(I) / s*HN (the lone pair
of an I atom and the antibonding orbital of an HN bond) and
(2) n(O) / s*PbI (the lone pair of an O atom and the antibonding
orbital of an PbI bond). The covalent bond between Pb and O
atoms when PbI2 is dissolved independently in the solvent is
replaced by hydrogen bonds in interaction (2). Comparing the
DMF- and DMAC-based situations, it can be seen that the
stabilization energy of the local interaction (2) between a CH3NH3PbI3 unit and DMAC is obviously smaller than that between
a CH3NH3PbI3 unit and DMF, which means that it is easier for
the CH3NH3PbI3 unit to escape from the solvent. Meanwhile,
interaction (1) between the organic and inorganic units in
CH3NH3PbI3 is stronger in DMAC, which is favorable to crystallization of the CH3NH3PbI3 lm. Fig. 7g shows the conguration of CH3NH3PbI3 away from the solvent. As shown in
Table 1, in CH3NH3PbI3, there are two major types of local
interactions; namely, (1) n(I) / s*HN (the same as in Fig. 6c and
f) and (2) n(I) / s*HC (the lone pair of an I atom and the antibonding orbital of an HC bond). Fig. 7h shows clear schematic
diagrams illustrating that when CH3NH3I and PbCl2 are dissolved in DMAC at the same time, CH3NH3I and PbCl2 can also
self-assemble to initially form the organicinorganic hybrid

Fig. 7 Schematic diagram of the solute solvent interactions.

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Table 1

Paper

Stabilization energy (in kcal mol
1) of main interactions between CH3CH3I, PbI2, PbCl2 and solvent molecule

Structure

PbI2
DMF

PbI2
DMAC

Donoraccept

Stabilization energy

BD (OPb)
n(O) / s*NH
sOC / s*NH
n(I) / s*NH
n(I) / s*NH
n(I) / s*NH
n(Cl) / s*NH
n(Cl) / s*NH
n(O) / s*PbI
n(I) / s*HC

269.20

CH3CH3I
DMF

CH3CH3I
DMAC

12.35
6.69
42.98

13.80
7.93
40.96

CH3CH3I
PbI2DMF

CH3CH3I
PbI2DMAC

CH3CH3I
PbCl2DMAC

19.88
9.53
9.03

19.34
9.94
9.29

15.74

CH3CH3PbI3

268.57

structure CH3NH3PbICl2. As shown in Table 1, there are three

major types of local interactions, namely, (1) n(I) / s*HN (the
lone pair of an I atom and the antibonding orbital of an
HN bond), (2) n(Cl) / s*HN (the lone pair of an Cl atom and
the antibonding orbital of an HN bond) and (3) n(O) / s*PbI
(the lone pair of an O atom and the antibonding orbital of an
PbI bond). We can be seen that the stabilization energy of the
local interaction (2) in CH3NH3PbICl2 is stronger than corresponding interaction (1) in CH3NH3PbI3. At the same time,
interaction (3) between a CH3NH3PbICl2 unit and DMAC is
obviously smaller, which means that it is dicult to replace Cl

with I
in the short term and CH3NH3PbICl2 can be le in an
unusable state. Thus, the existence of PbCl2 slows down the selfassemble of CH3NH3PbI3, which hinders CH3NH3PbI3 unit
escaping from the solvent and moreover does disadvantage to
the quick formation of CH3NH3PbI3 lms.
The above calculations suggest the following: DMAC is
favorable for the escape of CH3NH3PbI3 from the solvent and
subsequent crystallization; PbI2 and CH3NH3I diuse easily in
DMAC, and DMAC can be released quite quickly in the absence
of chlorine; the in situ self-assembly of perovskite crystals
between CH3NH3I and the PbI2 crystal lattice would follow
within a sucient volume of space. The DMAC-based depositioncrystallization method allows control of the dynamics of
nucleation and grain growth of CH3NH3PbI3, which facilitates
the formation of more uniform perovskite lms. Therefore, we
believe that the DMAC solution of CH3NH3PbI3 is more specifically suited to preparing high-quality perovskite lms with
good coverage and homogeneity.

Conclusions
We demonstrated that DMAC is an eective solvent for
controlling the dynamics of nucleation and grain growth of
CH3NH3PbI3, and it yields a smooth compact perovskite lm
with grains of dierent sizes. High-performance planarheterojunction devices were fabricated from these highquality perovskite thin lms, which exhibited an average
power-conversion eciency of 14.23% and a best eciency of
15.12%. On the contrary, the photovoltaic performance based

20528 | RSC Adv., 2015, 5, 2052120529

27.63

24.36

18.70
18.59

13.04
12.28
22.03
2.19

on perovskite lms prepared from the commonly used solvent

DMF was not high owing to the poor perovskite morphology. In
addition, we determined that the CH3NH3PbI3 lms based on
the solvent DMAC had better visible optical absorption, carrier
diusion length, and stability in air. Furthermore, the interactions and coordination between PbI2, CH3NH3I, and the solvent
molecules were revealed by simulations. Based on the calculated stabilization energies together with the kinetics of
CH3NH3PbI3 crystal growth, we conrmed that the DMAC-based
depositioncrystallization method enables the attainment of
higher optoelectronic characteristics for perovskite lms. We
thus conclude that DMAC is a more suitable solvent for the
preparation of the CH3NH3PbI3 precursor solution.

Acknowledgements
This work was supported by The Privileged Development
Program of Jiangsu High Education on New energy material
science and engineering, the National Natural Science Foundation of china (Grant no. 51272033), the Natural Science
Foundation of the Jiangsu Higher Education Institutions of
China (Grant no. 14KJA430001, EEKJA48000).

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